Chem 21 Fall 2009

Experiment 9 —

Recrystallization

_____________________________________________________________________________

Pre-lab preparation. (1) Read the supplemental material from Zubrick, The Organic Chem Lab
Survival Manual. (2) Draw the structure of acetanilide and report relevant physical data. Be
sure to cite the source of the data. You should be able to figure out what's relevant by reading
the procedure. (3) Find and report the boiling points of the solvents you will be using for this
experiment. (4) Outline the steps in the recrystallization of acetanilide.

Recrystallization involves dissolving a solid in a solvent and crystallizing it again, taking

Ideally, one would like to recover all of the desired solid completely free of
contaminants. Unfortunately, this is rarely possible. Usually, if most of the material is
recovered, it is not very pure, and extremely pure material can be obtained only in low yield.
The trick is to find the proper balance between yield and purity.

Now to the specifics of the problem at hand. Over the summer, certain stockroom
personnel had an unauthorized juggling contest and accidentally dumped all the acetanilide on
the floor. Unfortunately, the floor wasn't very clean, now the material is contaminated with what
appears to be rodent hair, gravel, dead spiders, etc. They were able to remove most of the dead
roaches. Your mission, should you decide to accept it... well, you really have no choice but to
accept it, do you?... is to clean up the acetanilide by recrystallizing it.

1
 Experiment 9 Fall 2009

Part A — acetanilide. Fetch about 1 g of dirty acetanilide. Don't fool around adjusting
the mass to 1.000g — it's not that important — just record in your notebook exactly how much
you used. Place your weighed sample in a 125-ml Erlenmeyer flask and add a boiling chip. Heat
about 50 ml of water to boiling in a separate flask (+ boiling chip!) using a hot plate.

Note: Always add a boiling chip before heating any solvent or solution. Never add
any solid to a liquid that is at or near its boiling point. Suddenly creating nucleation sites is
likely to cause anything from a simple boil-over to something resembling a volcano.

Now, dissolve the solid in a minimal amount of boiling water. This is done by adding the
solvent to the solute (not the other way around!) in small increments and bringing the solution to
a boil. Start out with about 10 - 15 ml of water and add a few ml at a time until all the soluble
stuff dissolves. (Don't measure it out, just estimate!) Watch how much solid dissolves each time
— this will give you an idea how much water you'll need to add to dissolve it all. Just be careful
not to add way too much water, or you'll have to reduce the volume later. And keep in mind that
there may be insoluble junk remaining after all the good stuff has dissolved. How do you tell the
difference? One bit of information is the color. What color is acetanilide? What color is the
stuff that's not dissolving? One final bit of advice — solids with melting points below the
boiling point of the solvent will melt and form what look like oil droplets. If you see this, you
need to add more solvent until the droplets dissolve. Even solids that melt above the solvent bp
may do this if they are very impure (remember mp depression?) or if the hot water can infiltrate
the crystal lattice

To get rid of the insoluble bits, filter the hot solution by gravity through a pre-warmed
funnel containing fluted filter paper. The tricky part is to keep the solution hot during this
operation. This is important — if you heat the solution, then remove it from the hot plate and try
to do the filtration on the benchtop, everything's going to cool down, right? Solid will precipitate
all over the place and make a terrible mess. Rinse the filter paper with a little hot solvent to
dissolve any crystals that may have formed.

Slow crystallization is the key to getting high purity product. Plunging the hot solution
into ice may cause tiny crystallites to crash out of solution (if it doesn't break the flask), and lots
of impurities will end up trapped in the crystal lattice. So don't do that. Instead, allow the

2
Experiment 9 Fall 2009

filtrate to cool sllloooooooowwwwly. Be patient. If the solution was close to the saturation
point when it was hot, the compound should be eager to crystallize as the solution cools. If no
crystals form, this could be because (1) the solution is too dilute (i.e. the solid is completely
soluble so it doesn't want to come out of solution), or (2) the solution is supersaturated (i.e. the
solid would like to crystallize but can't quite decide how to get started. If the problem is too
much solvent, the only remedy is to boil off the excess. If the solution is supersaturated, try
scratching the flask with a glass stirring rod — the scratches and glass chips may provide
nucleation sites that get crystal formation started. If that doesn't work, try adding a tiny seed
crystal. The best seed crystal is a tiny speck of someone else's clean solid. If you're not too
fussy about product purity, those white flakes in your instructor's beard can probably also be
used as seed crystals. Once crystal formation appears to have stopped, cool the flask in ice to
complete the crystallization. Collect the crystals by suction filtration using a Büchner funnel.
Wash the crystals with a few milliliters of cold water, and press them down with a clean spatula
or small beaker.

Dry the crystals by pressing them between two pieces of clean filter paper, and let them
dry until your next lab period. You will then determine the mass, the % recovery, and the
melting range.

Part B — solids from Extraction lab. You've saved samples of benzoic acid,
benzocaine, and fluorenone that we separated by extraction several weeks ago. Now we're going
to purify these by recrystallization. So that we have plenty of material to work with we're going
to start by consolidating samples with other groups.

Get together with two other groups, and combine your three samples of benzoic acid,
(separately!) combine your three samples of benzocaine, and combine your three samples of
fluorenone. (If you misread this and mix everything together, no worries, you can just repeat the
extraction to separate them again.)

Now, one group is going to recrystallize the benzoic acid from water, one group is going
to recrystallize the benzocaine from ethanol and water, and one group is going to recrystallize the
fluorenone from hexanes.

3
 Experiment 9 Fall 2009

You'll have to figure out how much solvent to use. Hot filtration should probably not be
necessary unless you have to sweep the solid up off the floor. The procedure for the mixed
solvent crystallization can be found in the supplemental reading from Zubrick.

Your purified solids will be dry enough by next week for a final melting point. Next
semester we'll measure their infrared spectra.

Your report for this lab consists of your data and observations for both parts that you did.
Also include a brief synopsis of the procedures used by the two groups with whom you
collaborated. For example, "W. Fu and G. Snyder recrystallized 4.27g of impure Lipitor that
they swept up off the floor. 15 ml of boiling benzene was used to dissolve the solid, and the hot
solution was filtered by gravity. Upon cooling... [describe the crystals and how they were
isolated]" If the solid is dry, you can measure the mass and % recovery now.

Turn this in before you leave, not next week, please. The management appreciates your
cooperation.